Use of quaternized derivatives of polymerized pyridines and quinolines as demulsifiers

ABSTRACT

This invention relates to alkylated derivatives of polymerized aromatic nitrogen heterocyclic compounds as illustrated by polymerized pyridine, quinoline and derivatives thereof; and uses thereof. 
     These compositions are polymerized by treating said aromatic nitrogen heterocyclic compounds at elevated temperatures and pressures with catalytic amounts of alkyl halides and the alkylating the polymerized products formed.

This is a division, of application Ser. No. 32,044, filed Apr. 23, 1979,and now allowed as U.S. Pat. No. 4,297,484.

In Ser. No. 32,037 filed Apr. 23, 1979, now allowed U.S. Pat. No.4,297,484 there is described and claimed a process for thepolymerization of aromatic heterocyclic nitrogen compounds includingpyridine and quinoline and derivatives thereof. Said applicationdescribed aromatic heterocycles such as quinolines and pyridines whichwhen heated to >250° C. with catalytic amounts of alkyl halides undergopolymerization. When the IR spectra are evaluated, probable structuresare the following. ##STR1## where

x+y=1-100 but preferably 1-10.

R=alkyl, OH, halogen.

POLYPYRIDINES

--CR=CR-CR=CR-CR=N)_(x)

where

x=1-100 but preferably 1-10

R=alkyl, halogen, aryl.

I have found that the resulting polyaromatic heterocycles such aspolyquinolines and polypyridines, when alkylated with alkyl halides,dimethyl sulfate and other alkylating agents form iminium salts. Thisreaction is well known and may be illustrated by the following generalequation. ##STR2## where p R=alkyl, aralkyl, alkenyl, alkynl, and thelike.

X=halogen, sulfate and the like.

Thus the reaction of polyquinoline with an alkyl halide may beillustrated by the following equation: ##STR3##

Similarly the reaction of polypyridine with an alkyl halide may beillustrated by the following equation: ##STR4##

The polyiminium salts of this invention are useful as corrosioninhibitors, microbiocides, water clarifiers, emulsion breakers of theoil-in-water class.

Non-limiting examples of heterocyclic aromatic compounds that can bepolymerized for utilization in this invention include quinoline,2-methyl quinoline, 4-methyl quinoline, pyridine, 2-methyl pyridine,4-methyl pyridine, 4-phenyl pyridine, 4-ethyl pyridine,2-hydroxypyridine, 2,4-lutidine and the like.

Alkylating agents include: methyl iodide, ethyl iodide, propyliodide,ethyl bromide, benzyl bromide, butyl bromide, dodecyl bromide, benzylchloride, dodecyl benzyl chloride, ethyl bromoacetate, dimethyl sulfateand the like.

The alkylation may be carried out in such aprotic solvents asdimethylformamide, dimethylsulfoxide, dimethylacetamide or mixtures ofthe aforementioned solvents with lower alcohols such as methanol,ethanol, 2-propanol and the like.

The following examples are illustrative of the present invention.

EXAMPLE 1

Polyquinoline, 12.9 g (0.1 eqv.) with a molecular weight of *580 wasdissolved with heating and stirring in 40 ml. of dimethyl formamide. Thesolution was cooled and 14.2 g (0.1 eqv.) of methyl iodide was added.The resulting solution was heated at 100° C. for 8 hrs. The DMF wasremoved by heating under reduced pressure leaving a red-brown solid thatwas soluble in a 50:50, by volume, mixture of water and ethanol.

Anal. %I calc.=46.86 %I found=47.21

H'n,m,r., solvent CDCl₃, reference T.M.S.,

τ=6.46 (N⁺ -CH₃).

The product consisted of the following structural species. ##STR5##

EXAMPLE 2

In a similar manner, polyquinoline (molecular weight of 580) 12.9 g (0.1eqv.) was reacted with 17.0 g (0.1 eqv.) of propyl iodide in 50 ml. ofdimethylformamide for 8 hrs. at 100° C. The product, soluble in amixture of water and ethyl alcohol, had the following structuralconfiguration. ##STR6##

EXAMPLE 3

In a similar manner, polyquinoline (molecular weight of 700) 12.9 g (0.1eqv.) was reacted at 120° C. with 24.9 g (0.1 eqv.) of dodecyl bromidein a mixture of 40 ml. of dimethylformamide and 10 ml. of n-propanol fora period of 16 hrs. The product, soluble in a mixture of water andethanol, had the following structural configuration. ##STR7##

EXAMPLE 4

In a similar manner, poly(4-methyl quinoline) 14.3 g (0.1 eqv.) having amolecular weight of 900, was reacted with 14.2 g (0.1 eqv.) of methyliodide in 50 ml. of dimethylsulfoxide for 8 hrs. at 100° C. The producthad the following structural configuration. ##STR8##

EXAMPLE 5

In a similar manner poly(2-methyl quinoline) 14.3 g (0.1 eqv.) having amolecular weight of 820, was reacted with 27.7 g (0.1 eqv.) oftetradecyl bromide at 130° C. in 50 ml. of dimethylformamide for 24hours. The product had the following structural configuration. ##STR9##

EXAMPLE 6

In a similar manner, polyquinoline (molecular weight of 580) 12.9 g (0.1eqv.) was reacted at 120° C. with 17.1 g (0.1 eqv.) of benzyl bromide ina mixture of 30 ml. of dimethylformamide and 10 ml. of n-propanol for 16hrs. The product had the following structural configuration. ##STR10##

EXAMPLE 7

Polypyridine, 7.9 g (0.1 eqv.) having a molecular weight *500 wasreacted with 14.2 g (0.1 eqv.) of CH₃ I in 40 ml. of dimethylformamideat 100° C. for 8 hrs. The product was a red-brown solid soluble inwater. It had the following structure:

Anal. %I calcd.=57.47; %I found=58.01.

EXAMPLE 8

Polypyridine 7.9 g (0.1 eqv.) with a molecular weight of 500 was reactedwith 24.9 g (0.1 eqv.) of dodecyl bromide for 16 hrs. at 100° C. in 50ml. of dimethylformamide. The product had the following structure.##STR12## To avoid repetitive details and to further illustrate theinvention, additional examples are summarized in the following table.

                                      TABLE 1                                     __________________________________________________________________________                            Alkylating                                            Example                                                                            Polypyridine       Agent  Structure of Product                           __________________________________________________________________________          ##STR13##         C.sub.6 H.sub.5 CH.sub.2 Cl                                                           ##STR14##                                     10   (CHCHCHCHCHN).sub.n                                                                              C.sub.14 H.sub.29 Br                                                                  ##STR15##                                     11   (CHCHCHCHCHN).sub.n                                                                              C.sub.8 H.sub.17 Br                                                                   ##STR16##                                     12                                                                                  ##STR17##         C.sub.10 H.sub.21 Br                                                                  ##STR18##                                     13   (CHCHCHCHCHN).sub.n                                                                              C.sub.3 H.sub.7 I                                                                     ##STR19##                                     14   (CHCHCHCHCHN).sub.n                                                                              (CH.sub.3).sub.2 SO.sub.4                                                             ##STR20##                                     __________________________________________________________________________

USES

This invention also relates to the inhibition of corrosion, particularlythe corrosion of metals in contact with the acid solutions.

The present invention is especially useful in the acidizing or treatingof earth formations and wells traversed by a bore hole. It may also beused in metal cleaning and pickling baths which generally compriseaqueous solutions of inorganic acids such as sulfuric acid, hydrochloricacid, phosphoric acid and are useful in the cleaning and treatment ofiron, zinc, ferrous alloys, and the like.

If no corrosion inhibitor is present when the aqueous acidic solutioncomes in contact with the metal, excessive metal loss and consumption orloss of acid, and other adverse results will be experienced. There hasbeen a continuing search for corrosion inhibitors which can be usedeffectively in small concentrations, and which are economical toproduce. The need is also for corrosion inhibitors which are effectiveat high temperatures, e.g., 200° F., and above, such as are found inoperations involving acidic solutions, particularly oil-well acidizingwhere higher and higher temperatures are found as the well extendsfurther into the earth.

While the compounds of this invention are of themselves particularlygood acid corrosion inhibitors, optionally they may be blended withacetylenic alcohols, dispersing and solubilizing agents such asethoxylated phenols, alcohols, and fatty acids. They may also be blendedwith such known acid inhibitors as the quinoline or alkyl pyridinequaternary compounds or synergists such as terpene alcohols, formamide,formic acid, alkyl amine, alkylene polyamines, heterocyclic amines, andthe like.

Quaternary ammonium compounds may be illustrated by C-alkylpyridine-N-methyl chloride quaternary, C-alkyl pyridine-N-benzylchloride quaternary, quinoline-N-benzyl chloride quaternary,isoquinoline-N-benzyl chloride quaternary, thioalkyl pyridinequaternaries, thioquinoline quaternaries, benzoquinoline quaternaries,thiobenzoquinoline quaternaries, imidazole quaternaries, pyrimidinequaternaries, carbazole quaternaries, the corresponding ammoniumcompounds, pyridines and quinolines may also be used alone or incombination with the quaternary compounds. Thus a pyridine plusquinoline quaternary, a quinoline plus quinoline quaternary, orquinoline or amine alone or in combination may be used.

The formic acid compound may be selected from the esters and amides offormic acid. The formic acid compound may be from the group consistingof formate esters of the structure:

    HCOOR

where R is a monoaryl group, an alkyl group having 1 to 6 carbon atoms,cyclo-alkyl residues having 5 to 6 carbon atoms, alkenyl and alkynlgroups having 2 to 6 carbon atoms which may contain functional groupingsselected from --C--OH, --OH, ═C═O, --COOH, --SH, and NH₂. Examples ofthe formic acid compound are: methyl formate, ethyl-formate, benzylformate, other alkyl and aryl formates, and the like. Other examplesinclude formamide, dimethyl formamide, formanilide, and the like.Mixtures of the esters and mixtures of the amides may be used.

USE IN ACIDIZING EARTH FORMATIONS

The compositions of this invention can also be used as corrosioninhibitors in acidizing media employed in the treatment of deep wells toreverse the production of petroleum or gas therefrom and moreparticularly to an improved method of acidizing a calcareous ormagnesium oil-bearing formation.

It is well known that production of petroleum or gas from a limestone,dolomite, or other calcareous-magnesian formation can be stimulated byintroducing an acid into the producing well and forcing it into the oilor gas bearing formation. The treating acid, commonly a mineral acidsuch as HCl, is capable of forming water soluble salts upon contact withthe formation and is effective to increase the permeability thereof andaugment the flow of petroleum to the producing well.

CORROSION TEST PROCEDURE

In these tests the acid solutions were mixed by diluting concentratedhydrochloric acid with water to the desired concentrations.

Corrosion coupons of 1020 steel (AISI) were pickled in an uninhibited10% HCl solution for 10 minutes, neutralized in a 10% solution ofNaHCO₃, dipped in acetone to remove water and allowed to dry. They werethen weighed to the nearest milligram and stored in a desicator.

In most of the tests, a 25 cc/in² acid volume to coupon surface arearatio was used. After the desired amount of acid was poured into glassbottles, the inhibitor was added. The inhibited acid solution was thenplaced in a water bath which had been set at a predetermined temperatureand allowed to preheat for 20 minutes. After which time, the couponswere placed in the preheated inhibited acid solutions. The coupons wereleft in the acid solutions for the specified test time, then removed,neutralized, recleaned, rinsed, dipped in acetone, allowed to dry, thenreweighed.

The loss in weight in grams was multiplied times a calculated factor toconvert the loss in weight to lbs./ft² /24 hrs. The factor wascalculated as follows: ##EQU1##

The inhibitor compositions were employed to inhibit corrosion in 15%hydrochloric acid. The tests were run at 150° F. for 4 hours. 0.2%, byvolume, inhibitor was employed. The results of the test are tabulated inthe table below.

                  TABLE 2                                                         ______________________________________                                        Example no. Corrosion rate (lbs./ft..sup.2 /day)                              ______________________________________                                        Blank       3.324                                                             1           0.087                                                             2           0.112                                                             3           0.052                                                             5           0.051                                                             6           0.035                                                             7           0.081                                                             8           0.043                                                             9           0.045                                                             ______________________________________                                    

WATER CLARIFICATION

This phase of the present invention relates to a method for theclarification of water containing suspended matter.

Accordingly clarification of water containing suspended particles ofmatter is effected by adding to such water compounds of this invention.

Water containing suspended particles which may be treated by the presentinvention may have its origin either in natural or artificial sources,including industrial and sanitary sources. Waters containing suspendedparticles of natural origin are usually surface waters, wherein theparticles are suspended soil particles (silt), although sub-surfacewaters may also be treated according to the present invention. Waterhaving its origin in industrial process (including sanitary water)operations may contain many different varieties of suspended particles.These particles are generally the result of the particular industrial orsanitary operation concerned. Prior to discharging such industrial wastewaters into natural water courses it generally is desired that thesuspended matter be removed.

The present process may likewise be applied to water contained in stockor fish ponds, lakes or other natural or artificial bodies of watercontaining suspended solids. It may be applied to industrial watersupplied either in preparation therefor, during or after use and priorto disposal. It may be applied to sanitary water supplies either for theelimination of suspended solids prior to use for such purposes, or itmay be applied to such waters which have become contaminated withimpurities from any source.

Most naturally occurring waters contain an amount of simple electrolytes(sodium, potassium, ammonium, calcium, aluminum salts, etc.) in excessof that necessary for the initial aggregation of the ultimate siltparticles. This is likewise true of particles of suspended material inindustrial or sanitary waters. The ultimate particles of silt or othermaterials are therefore naturally somewhat aggregated by reason of thepresence of such electrolytes. However, the forces binding such ultimateparticles together are not great and moreover are not such as togenerally effect either rapid settling rates of the flocculated materialor strong enough to prevent deflocculation.

The compounds of this invention cause rapid flocculation and alsoreinforce the formed aggregates of particles causing a generaltightening or bonding together of the initial particles and an increasedrate of coagulation and settling, thus forming a less turbid supernatantliquid.

The addition of the compounds of this invention to the water suspensionshould be made in such a fashion that the resulting flocculation andaggregation of the particles takes place uniformly throughout the bodyof water. In order to obtain a uniform addition of the compositions ofthe invention to the water-borne suspension it is generally desirable toprepare a relatively dilute stock solution of the compositions and thento add such solution to the body of water in the proportions indicated.Clarification may take place either in the natural body of water or itmay be caused to take place in hydraulic thickeners of known design.

The amount of the compositions to be employed will vary depending uponthe amount and the degree of subdivision of the solids to beagglomerated or flocculated, the chemical nature of such solid and theparticular inventive compositions employed. In general, we employ atleast a sufficient amount of the compositions to promote flocculation.In general, we employ 0.005-10,000 ppm or more such as about 0.5-1,000ppm, for example, about 1-500 ppm, but preferably about 2-5 ppm. Sincethe economics of these processes are important, no more than the minimumamount required for efficient removal is generally employed. It isdesired, of course, to employ sufficient compositions so flocculationwill take place without causing the formation of stable dispersions.

The precipitating action of the compositions can be employed in theapplication of loading or filling materials to textiles or paper.

In the processing of fine mineral particles in aqueous suspension theflocculating agents will be especially useful. In the processing of oresto separate valuable mineral constituents from undesirable matrixconstituents, it is frequent practice to grind the ore into a finelydivided state to facilitate separation steps such as selective flotationand the like. In many ore dressing procedures, the finely divided ore issuspended in water to form a pulp or slime. After processing, it isusually desirable to dewater the pulps or slimes either by sedimentationor filtering. In such operations, certain ores are particularlytroublesome in that the finely divided ore, when suspended in water,forms a stable slime which settles very slowly, if at all. Such slimesare unsuitable for concentration or dewatering by sedimentation and aredifficult to dewater by filtration because of the tendency to clog thepores of the filter, thus leading the excessively time-consuming andinefficient operation of the filters. In some cases, for example, incertain phosphate mining operations, the formation of very stablesuspensions of finely divided mineral results not only in the loss ofconsiderable valuable mineral as waste but also requires largeexpenditures for the maintenance of holding ponds for the waste. Similarproblems are involved in processing gold, copper, nickel, lead, zinc,iron, such as taconite ores, uranium and other ores, and the inventiveflocculating agents will be useful in these operations.

Some specific additional applications for the compositions of thisinvention, not intended to be limiting but merely illustrative arelisted below. The compositions can be used for the clarification ofbeers or wines during manufacture. Another use is in processingeffluents in pharmaceutical operations for the recovery of valuableproducts or removal of undesirable by-products. A particularly importantuse for these flocculating agents is in the clarification of both beetsugar and cane sugar juices in their processing. Still another use isfor flocculation and recovery of pigments from aqueous suspensionsthereof. The compositions will be particularly useful in sewagetreatment operations as a flocculating agent. A further use is topromote by flocculation the removal of coal from aqueous suspensionsthereof. In other words, the flocculating agents of the invention aregenerally useful for processing aqueous effluents of all types tofacilitate the removal of suspended solids.

A water soluble or water dispersible compound, to the extent ofeffective concentration, is employed.

These compositions can also be employed in the process of flocculatingwhite water and/or recycling of the precipitate solids in the papermaking process.

Although the manner of practicing the present invention is clear fromthe foregoing description, the following non-limiting specific examplesare included for purposes of illustration.

Naturally occurring water from many sources, and in some instances,brine and brackish waters are used in the recovery of petroleum bysecondary water-flooding operations. Clarification of the water isnecessary in many instances prior to water flooding because thesuspended impurities tend to plug the underground formations into whichwaters are pumped.

EXAMPLES

A suspension of FeS in brine was subjected to the action of thewater-soluble compounds prepared herein.

In these tests, the FeS concentration is 25 parts per million and 1 and5 percent brine solution were used. Metered quantities (500 ml.) of thehomogenous suspension were placed into 1,000 ml. beakers and stirred at100 rpm. The compound to be tested was injected into the suspension togive final active concentrations varying between 2 through 4 parts permillion. Stirring was achieved by use of a Phipp and Bird "floc"multi-stirrer. After 1 minute the stirring rate was reduced to 20 to 30rpm and maintained thus for 10 minutes. At this time the stirring wasstopped. The evaluation of the compound started at the moment offlocculation and continued with respect to the "floc" size and rate ofprecipitation. The final evaluation was achieved by visual examinationof the color of the resultant aqueous phase.

For example, example numbers 1, 2, 4, 7, 13, and 14, at 2 p.p.m., wereparticularly effective in regard to "floc" size, rate of precipitation,and final water clarity.

USE AS A MICROBIOCIDE (I) In water treatment

This phase of the present invention relates to the treatment of water.More particularly, it is directed to providing improved means forcontrolling microbiological organisms including bacteria, fungi, algae,protozoa, and the like, present in water.

It is well known that ordinary water contains various bacteria, fungi,algae, protozoa and other microbiological organisms which, ifuncontrolled, multiply under certain conditions so as to present manyserious problems. For example, in swimming pools the growth of thesemicrobiological organisms is very undesirable from a sanitary standpointas well as for general appearances and maintenance. In industrial watersystems such as cooling towers, condenser boxes, spray condensers, watertanks, basins, gravel water filters, and the like, miicrobiologicalorganisms may interfere greatly with proper functioning of equipment andresult in poor heat transfer, clogging of systems and rotting of woodenequipment, as well as many other costly and deleterious effects.

In other industrial applications where water is used in processes, asfor example, as a carrying medium, etc., microbiological organisms mayalso constitute a problem in maintenance and operation. Illustrative ofsuch industrial applications are the pulp and paper manufacturingprocesses, oil well flooding operations and the like.

The products of this invention are suitable as biocides for industrial,agricultural and horticultural, military, hygienic and recreationslwater supplies. They provide an inexpensive, easily prepared group ofproducts which can be used, in minimal amounts, in water supplies, incooling towers, air-conditioning systems, on the farm and ranch, in thefactory, in civilian and military hospitals and dispensaries, in camps,for swimming pools, baths and aquaria, waterworks, wells, reservoirs, byfire-fighting agencies, on maritime and naval vessels, in boilers,steam-generators and locomotives, in pulp and paper mills, forirrigation and drainage, for sewage and waste disposal, in the textileindustry, in the chemical industries, in the tanning industry, etcetera, and which will render said water supplies bactericidal,fungicidal and algicidal. They further provide a simple process wherebywater supplies, for whatever purposes intended, are renderedbacteriostatic, fungistatic and algistatic, i.e., said water suppliestreated by the process of this invention will resist and inhibit thefurther growth or proliferation of bacteria, fungi, algae and all formsof microbial life therein.

(II) WATER FLOODING IN SECONDARY RECOVERY OF OIL

This phase of the present invention relates to secondary recovery of oilby water flooding operations and is more particularly concenred with animproved process for treating flood water and oil recovery therewith.More particularly this invention relates to a process of inhibitingbacterial growth in the recovery of oil from oil-bearing strata by meansof water flooding taking place in the presence of sulfate-reducingbacteria.

Water flooding is widely used in the petroleum industry to effectsecondary recovery of oil. By employing this process the yield of oilfrom a given field may be increased beyond the 20-30 percent of the oilin a producing formation that is usually recovered in the primaryprocess. In flooding operation, water is forced under pressure throughinjection wells into or under oil-bearing formations to displace the oiltherefrom to adjacent producing wells. The oil-water mixture is usuallypumped from the producing wells into a receiving tank where the water,separated from the oil, is siphoned off, and the oil then transferred tostorage tanks. It is desirable in carrying out this process to maintaina high rate of water injection with a minimum expenditure of energy. Anyimpediment to the free entry of water into oil bearing formationsseriously reduces the efficiency of the recovery operation.

The term "flood water" as herein employed is any water injected into oilbearing formations for the secondary recovery of oil. In conventionaloperations, the water employed varies from relatively pure spring waterto brine and is inclusive of water reclaimed from secondary recoveryoperations and processed for recycling. The problems arising from thewater employed depend in part on the water used. However, particularlytroublesome and common to all types of water are problems directly orindirectly concerned with the presence of microorganisms, such asbacteria, fungi and algae. Microorganisms may impede the free entry ofwater into oil-bearing formations by producing ions susceptible offorming precipitates, forming slime and/or existing in sufficiently highnumbers to constitute an appreciable mass, thereby plugging the pores ofthe oil-bearing formation. Free-plugging increases the pressurenecessary to drive a given volume of water into an oil-bearing formationand oftentimes causes the flooding water to by-pass the formation to beflooded. In addition, microorganisms may bring about corrosion by actingon the metal structures of the wells involved, producing corrosivesubstances such as hydrogen sulfide, or producing conditions favorableto destructive corrosion such as decreasing the pH or producing oxygen.The products formed as the result of corrosive action may also bepore-plugging precipitates. Usually, the difficulties encountered are acombination of effects resulting from the activity of differentmicroorganisms.

(III) HYDROCARBON TREATMENT

This phase of the present invention relates to the use of thesecompounds as biocides in hydrocarbon systems.

In addition to being used as biocides in aqueous systems, the compoundsof this invention can also be employed as biocides in hydrocarbonsystems, particularly when petroleum products are stored. It is believedthat bacteria and other organisms, which are introduced into hydrocarbonsystems by water, feed readily on hydrocarbons resulting in a loss inproduct; that microorganisms cause the formation of gums, H₂ S,peroxides, acids and slimes at the interface between water and oil; thatbacterial action is often more pronounced with rolling motion than understatic conditions, etc. Loss of product, corrosion of the storage tank,clogging of filters and metering instruments, and fuel deterioration areamong the harmful effects of bacteria growth in fuels. The activity ofmicroorganism growth is often increased by the presence of rust. Notonly do these microorganisms often encourage rust but rust encouragesmicroorganism growth. Since microorganism growth appears to beconsiderably higher with kerosene than with gasoline, plugged filtersexperienced with jet fuels which contain large amounts of kerosene is aserious problem.

The compositions of this invention can be employed in hydrocarbonsystems.

MICROBIOCIDAL TESTING

The screening procedure was as follows: a one percent by weight solutionof the test compound in water was prepared. The solution was asepticallyadded to a sterile broth that would support the growth of the testorganism, Desulfovibro desulfuricans, to provide a concentration of 25,50 and 100 parts by weight of test compound per million parts by weightof broth. A general growth medium, such as prescribed by the AmericanPetroleum Institute was used. The broth containing the test compoundthen was dispersed in 5 cc. amounts into sterile disposable tubes andthe tubes were inoculated with the growing test organism and incubatedat 35° C. for 24 hours. The absence or presence of growth of themicroorganisms was determined by visual inspection by an experiencedobserver.

Following is a summary of the results of the testing of examples of thisinvention.

    ______________________________________                                                      Concentration of                                                Compound      test compound,                                                  example number                                                                              p.p.m.       Results                                            ______________________________________                                        3             50           Gave control..sup.1                                5             25           "                                                  8             50           "                                                  10            25           "                                                  ______________________________________                                         .sup.1 By control is meant that the test compound was biostatic or            biocidali.e., no growth of the test organism occurred under the test          conditions.   cl BREAKING EMULSIONS OF THE OIL-IN-WATER CLASS            

This phase of the present invention relates to a process for resolvingor separating emulsions of the oil-in-water class, by subjecting theemulsion to the action of the compositions of this invention.

Emulsions of the oil-in-water class comprise organic oily materials,which, although immiscible with water or aqueous or non-oily media, aredistributed or dispersed as small drops throughout a continuous body ofnon-oily medium. The proportion of dispersed oily material is in manyand possibly most cases a minor one.

Oil-field emulsions containing small proportions of crude petroleum oilrelatively stably dispersed in water or bring are representativeoil-in-water emulsions. Other oil-in-water emulsions include: steamcylinder emulsions, in which traces of lubricating oil are founddispersed in condensed steam from steam engines and steam pumps;wax-hexane-water emulsions, encountered in de-waxing operations in oilrefining; butadiene tar-in-water emulsions, in the manufacture ofbutadiene tar-in-water emulsions, in the manufacture of butadiene fromheavy naphtha by cracking in gas generators, and occurring particularlyin the wash box waters of such systems; emulsions of "flux oil" in steamcondensate produced in the catalytic dehydrogenation of butylene toproduce butadiene; styrene-in-water emulsions, in synthetic rubberplants; synthetic latex-in-water emulsions, in plants producingcompolymer butadiene-styrene or GR-S synthetic rubber; oil-in-wateremulsions occurring in the cooling water systems of gasoline absorptionplants; pipe press emulsions from steam-actuated presses in clay pipemanufacture; emulsions or petroleum residues-in diethylene glycol, inthe dehydration of natural gas.

In other industries and arts, emulsions of oily materials in water orother non-oily media are encountered for example, in synthetic resinemulsion paint formulation, milk and mayonnaise processing, marineballast water disposal, and furniture polish formulation. In cleaningthe equipment used in processing such products, diluted oil-in-wateremulsions are inadvertently, incidentally, or accidentally produced. Thedisposal of aqueous wastes is, in general, hampered by the presence ofoil-in-water emulsions.

Essential oils comprise non-saponifiable materials like terpenes,lactones, and alcohols. They also contain saponifiable esters ormixtures of saponifiable and non-saponifiable materials. Steamdistillation and other production procedures sometimes causeoil-in-water emulsions to be produced, from which the valuable essentialoils are difficultly recoverable.

In all such examples, a non-aqueous or oily material is emulsified in anaqueous or non-oily material with which it is naturally immiscible. Theterm "oil" is used herein to cover broadly the water-immisciblematerials present as dispersed particles in such systems. The non-oilyphase obviously includes diethylene glycol, aqueous solutions, and othernon-oily media in addition to water itself.

The foregoing examples illustrate the fact that, within the broad genusof oil-in-water emulsions, there are at least three importantsub-genera. In these, the dispersed oily material is respectivelynon-saponifiable, saponifiable, and a mixture of non-saponifiable andsaponifiable materials. Among the most important emulsions ofnon-saponifiable material in water are petroleum oil-in-water emulsions.Saponifiable oil-in-water emulsions have dispersed phases comprising,for example, saponifiable oils and fats and fatty acids, and othersaponifiable oily or fatty esters and the organic components of suchesters to the extent such components are immiscible with aqueous media.Emulsions produced from certain blended lubricating compositionscontaining both mineral and fatty oil ingredients are examples of thethird sub-genus.

Oil-in-water emulsions contain widely different proportions of dispersedphase. Where the emulsion is a waste product resulting from the flushingwith water of manufacturing areas or equipment, the oil content may beonly a few parts per million. Resin emulsion paints, as produced containa major proportion of dispersed phase. Naturally-occurring oil-fieldemulsions of the oil-in-water class carry crude oil in proportionsvarying from a few parts per million to about 20%, or even higher inrare cases.

The present invention is concerned with the resolution of theseemulsions of the oil-in-water class which contain a minor proportion ofdispersed phase, ranging from 20% down to a few parts per million.Emulsions containing more than about 20% of dispersed phase are commonlyof such stability as to be less responsive to the presently disclosedreagents, possibly because of the appreciable content of emulsifyingagent present in such systems, whether intentionally incorporated forthe purpose of stabilizing them, or not.

Although the present invention relates to emulsions containing as muchas 20% dispersed oily material, many if not most of them containappreciably less than this proportion of dispersed phase. In fact, mostof the emulsions encountered in the development of this invention havecontained about 1% or less of dispersed phase. It is to suchoil-in-water emulsions having dispersed phase volumes of the order of 1%or less to which the present process is particularly directed. This doesnot mean that any sharp line of demarcation exists, and that, forexample, an emulsion containing 1.0% of dispersed phase will respond tothe process, whereas one containing 1.1% of the same dispersed phasewill remain unaffected; but that, in general, dispersed phaseproportions of the order of 1% or less appear most favorable forapplication of the present process.

In emulsions having high proportions of dispersed phase, appreciableamounts of some emulsifying agent are probably present, to account fortheir stability. In the case of more dilute emulsions, containing 1% orless of dispersed phase, there may be difficulty in accounting for theirstability on the basis of the presence of an emulsifying agent in theconventional sense. For example, steam condensate frequently containsvery small proportions of refined petroleum lubricating oil in extremelystable dispersions; yet neither the steam condensate nor the refinedhydrocarbon oil would appear to contain anything suitable to stabilizethe emulsion. In such cases, emulsion stability must probably bepredicated on some basis other than the presence of an emulsifyingagent.

The present process, as stated above, appears to be effective inresolving emulsions containing up to about 20% of dispersed phase. It isparticularly effective on emulsions containing not more than 1% ofdispersed phase, which emulsions are the most important, in view oftheir common occurrence.

Some emulsions are by-products of manufacturing procedures, in which thecomposition of the emulsion and its ingredients is known. In manyinstances, however, the emulsions to be resolved are eithernaturally-occurring or accidentally or unintentionally produced; or inany event they do not result from a deliberate or premeditatedemulsification procedure. In numerous instances, the emulsifying agentis unknown; and as a matter of fact an emulsifying agent in theconventional sense, may be felt to be absent. It is obviously verydifficult or even impossible to recommend a resolution procedure for thetreatment of such latter emulsions, on the basis of theoreticalknowledge. Many of the most important applications of the presentprocess are concerned with the resolution of emulsions which are eithernaturally-occurring or are accidentally, unintentionally, or unavoidablyproduced. Such emulsions are commonly of the most dilute type,containing about 1% or less of dispersed phase, although concentrationsup to 20% are herein included, as stated above.

The process which constitutes the present invention comprises subjectingan emulsion of the oil-in-water class to the action of a reagent ordemulsifier of the kind herein described, thereby causing the oilparticles in the emulsion to coalesce sufficiently to rise to thesurface of the non-oily layer (or settle to the bottom, if the oildensity is greater), when the mixture is allowed to stand in thequiescent state after treatment with the reagent or demulsifier.

In operating the present process to resolve an oil-in-water emulsion,the reagent is introduced at any convenient point in the system, and itis mixed with the emulsion in any desired manner, such as by beingpumped or circulated through the system or by mechanical agitation suchas paddles, or by gas agitation. After mixing, the mixture of emulsionand reagent is allowed to stand quiescent until the constituent phasesof the emulsion separate. Settling times and optimum mixing times will,of course, vary with the nature of the emulsions and the apparatusavailable. The operation, in its broadest concept, is simply theintroduction of the reagent into the emulsion, the mixing of the two toestablish contact and promote coalescence, and, usually, the subsequentquiescent settling of the agitated mixture, to produce the aqueous andnon-aqueous emulsion phases as stratified layers.

Agitation may be achieved in various ways. The piping system throughwhich the emulsion is passed during processing may itself supplysufficient turbulence to achieve adequate mixing of reagent andemulsion. Baffled pipe may be inserted in the flow sheet to provideagitation. Other devices such as perforated-chamber mixters, excelsior-or mineral- or gravel- or steel-shaving-packed tanks, beds or stones orgravel or minerals in open ducts or trenches may be employedbeneficially to provide mixing. The introduction of a gas, such asnatural gas or air, into a tank or pipe in which or through which themixture of reagent and emulsion is standing or passing is frequentlyfound suitable to provide desired agitation.

It has been found that the factors, reagent feed rate, agitation andsettling time are somewhat inter-related. For example, with sufficientagitation of proper intensity the settling time required can bematerially shortened. On the other hand, if agitation is relativelynon-procurable but extended settling time is, the process may be equallyproductive of satisfactory results. The reagent feed rate has an optimumrange, which is sufficiently wide, however, to meet the tolerancesrequired for the variances encountered daily in commercial operations.

Application of a suitable gas in a procedure approximating that of thefroth flotation cell employed in ore beneficiation, after the presentreagent has been added to the emulsion to be resolved, frequently has afavorable influence of totally unexpected magnitude. By incorporatingthe step of subjecting the chemicalized emulsion to the action of air ina sub-aeration type flotation cell, a clear aqueous layer is sometimesobtained in a matter of seconds, without added quiescent settling, andwith approximately as much reagent as used in a companion test in whichno agitation was used. Such companion test separated a clear aqueouslayer only after standing quiescent for hours. Natural gas was found tobe as good a gaseous medium as was air in this operation.

It should be distinctly understood that such aeration technique, whilean important adjunct to the use of the present reagent, in some cases,is not an equivalent procedure. This may be proved by subjecting anunchemicalized emulsion to aeration for a period of minutes withoutdetectable favorable effect. Addition of the reagent to such aeratedemulsion will produce resolution, promptly.

The details of the mechanical structures required to produce aerationsuitable for the present purpose need not be given here. It issufficient to state that any means capable of producing small gasbubbles within the body of the emulsion is acceptable for use.

The order in which the reagent and the aeration step are applied isrelatively immaterial. Sometimes it is more convenient to chemicalizethe emulsion and subsequently to apply the aeration technique. Inothers, it may be more advantageous to produce a strongly frothingemulsion and then introduce the reagent into such aerated emulsion.

As stated previously, any desired gas can be substituted for air. Othercommonly suitable gases include natural, gas nitrogen, carbon dioxide,oxygen, etc., the gas being used essentially for its levitation effect.If any gas has some deleterious effect on any component of the emulsion,it will obviously be desirable to use instead some other gas which isinert under the conditions of use.

Although heat is ordinarily of little importance in resolvingoil-in-water class emulsions with my reagent, there are some instanceswhere heat is a useful adjunct. This is especially true where theviscosity of the continuous phase of the emulsion is appreciably higherthan that of water.

In some instances, importantly improved results are obtained byadjusting the pH of the emulsion to be treated, to an experimentallydetermined optimum value.

The reagent feed rate also has an optimum range, which is sufficientlywide, however, to meet the tolerances required for the variancesencountered daily in commercial operations. A large excess of reagentcan produce distinctly unfavorable results.

The reagents may be employed alone, or they may in some instances beemployed to advantage admixed with other compatible oil-in-waterdemulsifiers.

The process is commonly practiced simply by introducing smallproportions of the reagent into an oil-in-water class emulsion,agitating to secure distribution of the reagent and incipientcoalescence, and letting the mixture stand until the oil phaseseparates. The proportion of reagent required will vary with thecharacter of the emulsion to be resolved. Ordinarily, proportions ofreagent required are from about 1 ppm to about 500 ppm the volume ofemulsion treated, but more or less may be required in specifiedinstances. Preferably from about 10 ppm to 100 ppm is employed.

A preferred method of practicing the process to resolve a petroleumoil-in-water emulsion is as follows: Flow the oil well fluids,consisting of free oil, oil-in-water emulsion, and natural gas, througha conventional gas separator, then to a conventional steel oil-fieldtank, of, for example, 5,000-bbl. capacity. In this tank theoil-in-water emulsion falls to the bottom, is withdrawn, and is soseparated from the free oil. The oil-in-water emulsion, so withdrawn, issubjected to the action of the reagent in the desired small proportion,injection of reagent into the stream of oil-in-water emulsion beingaccomplished by means of a conventional proportioning pump or chemicalfeeder. The proportion employed in any instance is determined bytrial-and-error. The mixture of emulsion and reagent then flows to apond or sump wherein it remains quiescent and the previously emulsifiedoil separates, rises to the surface and is removed. The separated water,containing relatively little to substantially none of the previouslyemulsified oil, is thereafter discarded.

FIELD EXAMPLES

The compositions of this invention were very effective in the resolutionof oil-in-water emulsions.

A. In a California oil lease compounds of Examples 1 and 7 converted o/wpetroleum emulsions to clear water in concentrations of 10 ppm.

B. In a Wyoming oil field, the compounds of Example 2 converted an o/wpetroleum emulsion to clear water at 25 ppm.

I claim:
 1. A process of demulsification which comprises treating anemulsion system with a quaternized derivative of polymerized pyridine orquinoline compounds, which compounds prior to polymerization areselected from the group consisting of pyridine, 2-methyl pyridine,4-methyl pyridine, 4-phenyl pyridine, 4-ethyl pyridine,2-hydroxypyridine, 2,4-lutidine, quinoline, 2-methyl quinoline and4-methyl quinoline, the nitrogen atoms of which are quaternized bytreating said polymerized compounds with a quaternizing agent selectedfrom the group consisting of methyl iodide, ethyl iodide, propyl iodide,ethyl bromide, benzyl bromide, butyl bromide, dodecyl bromide, benzylchloride, dodecyl benzyl chloride, ethyl bromoacetate, dimethyl sulfate,tetradecyl bromide, and octyl bromide.
 2. The process of demulsificationof claim 1 wherein the quaternizing agent is benzyl chloride or benzylbromide.
 3. The process of demulsification of claim 1 wherein thequaternizing agent is selected from the group consisting of methyliodide, ethyl iodide, propyl iodide, ethyl bromide, butyl bromide,dodecyl bromide, tetradecyl bromide and dimethyl sulfate.
 4. The processof demulsification of claim 3 wherein the compound prior topolymerization is quinoline and the quaternizing agent is methyl iodide.5. The process of demulsification of claim 3 wherein the compound priorto polymerization is pyridine and the quaternizing agent is methyliodide.
 6. The process of demulsification of claim 3 wherein thecompound prior to polymerization is quinoline and the quaternizing agentis propyl iodide.
 7. The process of demulsification of claim 1 whereinthe emulsion system is an oil-in-water emulsion.
 8. The process ofdemulsification of claim 2 wherein the emulsion system is anoil-in-water emulsion.
 9. The process of demulsification of claim 3wherein the emulsion system is an oil-in-water emulsion.
 10. The processof demulsification of claim 4 wherein the emulsion system is anoil-in-water emulsion.
 11. The process of demulsification of claim 5wherein the emulsion system is an oil-in-water emulsion.
 12. The processof demulsification of claim 6 wherein the emulsion system is anoil-in-water emulsion.